US3346510A - Catalyst compositions and process for preparation thereof - Google Patents

Catalyst compositions and process for preparation thereof Download PDF

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Publication number
US3346510A
US3346510A US474996A US47499665A US3346510A US 3346510 A US3346510 A US 3346510A US 474996 A US474996 A US 474996A US 47499665 A US47499665 A US 47499665A US 3346510 A US3346510 A US 3346510A
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United States
Prior art keywords
component
acidic
catalyst
hydrogenation
alumina
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US474996A
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English (en)
Inventor
John H Sinfelt
William F Taylor
George W Dembinski
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Priority to US474996A priority Critical patent/US3346510A/en
Priority to GB30852/66A priority patent/GB1146543A/en
Priority to DE19661542122 priority patent/DE1542122A1/de
Priority to FR70765A priority patent/FR1487713A/fr
Priority to NL6610507A priority patent/NL6610507A/xx
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers

Definitions

  • the present invention relates to improved bifunctional catalysts containing a hydrogenation-dehydrogenation component and an acidic component, said catalyst composition being distinguished by the fact that said two components are held in relatively close physical proximity to each other but in such manner that chemical interaction between the two components is prevented.
  • the catalyst compositions of the present invention exhibit greater dehydrogenation activity and greater total acidic activity than the bifunctional catalysts previously known to the art. Additionally, the catalyst compositions of the present invention show a high selectivity towards the formation of commercially desirable products in the hydrocarbon conversion processes in which they are employed.
  • hydrocracking may be applied to virgin and catalytic naphthas, gas oils, cycle oils and stocks from conventional cracking operations boiling generally in the gas oil range, and alkyl aromatic hydrocarbons in general, as well as straight run heavy virgin naphthas and gas oils.
  • the hydrocarbon cracking process itself consists of passing the feedstock in admixture with hydrogen over the catalyst if a fixed bed of catalyst is used, or in contact with a moving bed or a fluidized solids bed of catalyst at suitable temperatures, feed rates, pressures, etc., to effect a substantial conversion of the freedstock to lower boiling materials, e.g., gasoline. Simultaneously, organic nitrogen and sulfur components present in the feed are largely converted to ammonia and hydrogen sulfide, respectively.
  • the reaction conditions are to a considerable extent governed by the nature of the feed, the activity of the catalyst, and the nature of the desired end product.
  • catalysts have been found to be particularly sensitive to the presence of feed impurities, in particular to organic nitrogen. Such catalysts include the oxides, sulfides and reduced forms of iron group metals. These catalysts require frequent regeneration, or maintenance of reaction conditions not conducive to high yields of desirable products.
  • Other catalysts such as noble metals supported on conventional amorphous cracking catalysts such as silica-alumina, silicamagnesia, silica-alumina-magnesia and the like, had not shown as high an activity as is desirable, and often require regeneration more often than desirable. Many catalysts also have high coke-forming tendencies, and also require relatively high pressures, which is expensive, as well as the requirement of feed purification to achieve desired activity levels.
  • crystalline metallic alumino-silicates having uniform pore openings of between 6-15 Angstroms.
  • These alumino-silicates have been given the designation of molecular sieves for their ability to selectively adsorb molecules of hydrocarbons having critical cross sectional molecular areas while excluding all larger hydrocarbons.
  • U.S. 2,971,903 described crystalline metallic alumino-silicates which contain a member of the alkaline earth, platinum or iron groups, or chromium.
  • the metal may be introduced into the crystalline alumino-silicate by ion exchange followed by reduction of the metal to its active form as in British Patent No. 941,349; or the metal component may be impregnated onto the molecular sieve as in French Patent No. 1,320,007.
  • Other methods suggested by the art for introducing metals into molecular sieves include treating the dehydrated molecu lar sieve with the vapor of the desired metal as in Belgian Patent No. 581,953 or alternatively utilizing a decomposable compound of the metal in question, which compound is adsorbed into the interstices of the sieve and decomposed therein, as in U.S. Patent No. 3,013,988.
  • the desired separation between the hydrogenation-dehydrogenation metal component and the strongly acid sites of the acidic component of the bifunctional catalyst is obtained by first treating the component containing the strongly acidic sites with a basic compound which will react reversibly and preferentially with said strongly acidic sites.
  • the base treated component may then be contacted with the hydrogenation-dehydrogenation component by any of the methods known to the art, such as wet impregnation, base exchange, etc., and the said hydrogenation-dehydrogenation component will interact selectively with the less acidic sites on the base treated acidic component.
  • the strongly acidic sites can be reactivated by removal of the base compound either as a separate step or in conjunction with the activation procedure for the hydrogenation-dehydrogenation metal component, e.g., during the reduction of said metal component from its oxide, sulfide or other high oxidation state to its metallic state.
  • Acidic components of the present catalyst compositions consist of acidic refractory oxides such as silica-alumina or halogen treated alumina, the aluminum halides and the aluminosilicate crystalline zeolites, either natural or synthetic, known to the art as molecular sieves.
  • acidic refractory oxides such as silica-alumina or halogen treated alumina, the aluminum halides and the aluminosilicate crystalline zeolites, either natural or synthetic, known to the art as molecular sieves.
  • the choice of which acidic component to use will of course depend upon the nature of the hydrocarbon conversion process contemplated, as the activity of each of said materials in 3 particular hydrocarbon conversion processes has been well established in the art.
  • Crystalline alumino-silicate zeolites that have molecular sieve properties are now Well known in the art. While the molecular sieve zeolites difier from each other in chemical composition, they may generally be characterized as alkali metal or alkaline earth metal, hydrated alumino-silicates. Their crystal patterns are such that they present structures containing a large number of pores having an exceptional uniformity of size. The pores in difierent zeolites may vary in diameter from less than 4 Angstroms to 15 Angstrom or more; but for any one of these zeolites, the pores are essentially of uniform size. Because of this, such zeolites are popularly known as molecular sieves.
  • Molecular sieve zeolites that have pore openings in the range of about 6 to 15 Angstroms can be employed as catalysts or catalyst bases for various processes, particularly hydrocarbon conversion processes, because the pore sizes are such that they allow for easy ingres of hydrocarbon reactants and egress of the reaction products.
  • the crystalline molecular sieve zeolites have chemical formulas whose anhydrous form may be expressed in terms of moles by the following:
  • Me is selected from the group consisting of metal cations and hydrogen, the metal cations being selected from the group consisting of cobalt, nickel, zinc, magnesium, calcium, cadmium, copper, barium and the rare earth metals.
  • the sieve as found in nature or prepared synthetically, will contain sodium as the metal cation. It is desirable to exchange the major portion of this sodium, i.e., to a final sodium concentration of less than 10 percent, by utilizing base-exchange processes well known in the art.
  • n is the valance of Me
  • X is a numher in the range from about 2 to about 14. Most useful are those zeolites in which X is in the range from about 3 to about 6.5.
  • Preferred molecular sieve zeolites for use in hydrocarbon conversion processes such as hydrocracking, hydroisomerization, hydrodenitrogenation, hydrodesulphurization, etc., are represented by synthetic faujasites or 13Y molecular sieves which have been cation exchanged to yield the hydrogen or magnesium form.
  • Other preferred molecular sieve zeolites are the 13X type, cation exchanged to yield the hydrogen, magnesium or rare earth element form.
  • the hydrogenation-dehydrogenation component utilized in the present invention comprises metals either in the elemental form or as the respective sulphides, oxides or other compounds decomposable to the elemental form of Group VIII metals in the Periodic Table as well as metals in any of the above forms of Groups VB, VI-B and VIIB or mixtures thereof.
  • the preferred metals for use in this component are members of the platinum family, e.g., platinum, palladium and nickel.
  • the bases which may be utilized to reversibly react with strong acid sites of the acidic component may be a Lewis type base, preferably a nitrogen containing compound.
  • suitable nitrogen compounds include the primary, secondary and tertiary alkyl amines, the aryl amines, the alkaryl amines, the arylalkylamines, the cycloalkylamines and ammonia.
  • Non-nitrogen containing bases may also be employed in the practice of the present invention as for example the substituted phosphorous compounds, e.g., phosphines. However, the nitrogen compounds are preferred.
  • Specific nitrogen compounds usable in the base treatment proces of the present invention include ammonia, methylamine, dimethylamine, ethylamine, diethylamine, the propylamines (including the iso compounds), the butylamines (including the iso and tertiary compounds), benzylamine, aniline, pyridine, quinoline, etc.
  • Ammonia is an especially preferred compound due to its ease of handling, cheapness and reactive properties.
  • the amount of base utilized can be in the range of l lO to l 10 g.-equivalents of base per square meter of surface of the acidic material; and preferably in the range of 0.5 to 3l l0 g.-equivalents of base per square meter of surface of acidic material.
  • the most preferred base is ammonia which in a preferred embodiment is used in the gaseous phase to neutralize the strongly acidic sites.
  • Ammonia can be desorbed from the acidic component with facility by treating at elevated temperatures, i.e., to 1200 F. at atmospheric or reduced pressures for 0.5 to 10 hours, which thermal treatment results in the desorption of the ammonia thereby restoring the original strongly acid sites.
  • the removal of the basic compound can be done as a separate step or can be done simultaneously with the activation of the hydrogenation-dehydrogenation component.
  • Example 1 A 100 gram sample of silica-alumina (87% SiO 13% A1 0 was dried for 4 hours at 220 F. and then was exposed to an ammonia vapor (0.08 gram of NH at room temperature for 1 hour. This neutralized material was impregnated with a sufficient quantity of a saturated aqueous solution of a nitro amino-platinum complex to ensure a 0.6 weight percent concentration of platinum metal in the finished catalyst, dried at 220 F. for 1 hour, and was subsequently reduced with hydrogen at 850 F.
  • Example 2 The catalyst composition prepared by the method of Example 1 was tested for catalytic activity at hydrocracking conditions on a n-heptane feedstream. For comparison sake, an identical catalyst composition was prepared with the exception that the platinum component was impregnated directly onto the silica-alumina component without the ammonia pretreatment. The result of this comparison test is given in Table I.
  • the catalyst prepared by the technique of the present invention proves to be approximately per cent more active overall than the conventional platinum on silica-alumina catalyst (54.0 vs. 46.8 percent total conversion).
  • the catalyst of the present invention was shown to be about 40% more active for the aromatization reaction and more active for the isomerization reaction. This indicates a higher activity at both the hydrogenation-dehydrogenation and acidic sites on the catalyst.
  • improved bifunctional catalysts can be prepared by utilizing a hydrogenation-dehydrogenation metal impregnated on a nonacidic component physically mixed with separate particles comprising the acidic component. In this manner, it is also possible to prevent the undesired interaction between the hydro genation-dehydrogenation metal and the strongly acidic sites of the acidic component.
  • the catalyst composition of this second embodiment of the instant invention can be prepared by mixing together separate particles, one of which contains the hy -drogenation-dehydrogenation active component prefer ably on a comparatively non-acidic support material, and the other an acidic component thereby forming a mixed catalyst in which the properties of the total catalyst are greatly superior to that which is obtained by indiscriminately introducing both components on the same particle, for example, by impregnating an untreated acidic support directly with the hydrogenation-dehydrogenation metal component.
  • the preparation of the mixed bifunctional catalyst of the above embodiment involves placing the hydrogenation-dehydrogenation metal on a non-acidic support material by means known to the art, e.g., by wet impregnation from an aqueous solution of a soluble form of the metal component.
  • the hydrogenation-dehydrogenation component used in this embodiment is selected from the group utilized in the single particle embodiment of the present invention, which have been describd prviously.
  • the support material for the dehydrogenation-hydrogenation metal component may be selected from relatively non-acidic refractory oxides such as alumina, silica, desurfaced silica-alumina, titania, zirconia and thoria.
  • a particularly preferred support material is alumina.
  • the bifunctional catalyst is obtained by simply mixing the supported hydrogenation-dehydrogenation component with the acidic component selected from the group pre' viously described for the single particle embodiment. It is preferred that both components be in the form of fine powders (about 48 to 325 Tyler mesh) to ensure close physical proximity of the two components in the final composition. After mixing, the bifunctional catalyst composition can be formed into any desired shape, e.g., by pelleting. It has been unexpectedly found that the ratio of the two components forming the mixed bifunctional catalyst must be within a critical range in order to obtain desirbale hydrocarbon conversion activity. This ratio is not proportional to the amount of hydrogenation-dehydrogenation metal component present in the mixture as would be generally expected. In particular, the ratio of acidic components to hydrogenation-dehydrogenation components should be greater than about 2 and less than about 99 to 1, preferably in the range between about 4 to about 19 to 1 and most preferably in the range between about 4 and 9 to l.
  • Hydrocracking activity expressed as percent yield to propane plus butanes when reacting n-heptane and hydrogen at SgOg/ffi, 200 p.s.i.g., 20 w./hr./w. and H2/!l-C7 mole ratio 0'
  • Example 3 TABLE III Dehydrogenation activity 1 0.6 wt. percent Pt on nonacidic A1 0 7 19 0.6 wt. percent Pt on acidic silica-alumina 2 1
  • Dehydrogenati-on activity expressed as percent conversion of cyclohexane to benzene at 600 F., 1 atm., 100 w./hr./w. and HQ/HC ratio of 4/1.
  • Example 4 pregnated with an aqueous solution of chloroplatinic ,3 acid to yield a constant total platinum level.
  • the catalyst mixtures were prepared by physically mixing the platinum/alumina and H-faujasite both in the form of fine powders (about 100 mesh), followed by pelleting the mixed powders into As-inch cylinders.
  • the platinum/alumina component was prepared using eta alumina as the support and was calcined in air at 1100 F. for one hour after impregnation.
  • the hydrogen faujasite was prepared from a synthetic 13 Y ammonium faujasite by heating the ammonium faujasite slowly in moist air while maintaining the temperature below 300 F. for the first three hours. All catalyst compositions were then reduced in hydrogen at 850 F. prior to the catalytic test, which reduction treatment resulted in converting the ammonium faujasite to the hydrogen form.
  • An improved bifunctional catalyst composition for hydrocarbon conversion processes comprising a hydrogenation-dehydrogenation component and an acidic component having reactive acidic sites of varying degrees of acidity thereon and selected from the group consisting of amorphous silica-alumina and the crystalline aluminasilicate zeolites having uniform pores in the range of 6 to 15 Angstroms wherein said components are maintained in close physical proximity to each other without concomitant chemical interaction between them said catalyst being prepared by first treating the acid component with a Lewis type base selected from the group consisting of the nitrogen containing bases and the phosphorus containing bases under conditions such that the said base selectively and reversibly interacts with the acidic sites having a greater degree of acidity, then compositing the hydrogenation-dehydrogenation component on the treated acidic component and reactivating the acidic sites by removing the basic compound from said acidic sites.
  • a Lewis type base selected from the group consisting of the nitrogen containing bases and the phosphorus containing bases under conditions such that the said base selectively and
  • An improved bifunctional catalyst composition comprising an acidic crystalline alumino-silicate zeolite having uniform pores in the range of 6 to 15 Angstroms, which zeolite is characterized further by having reactive acid sites of varying degrees of acidity thereon, wherein a hydrogenation-dehydrogenation metal catalyst component is selectively associated with the reactive sites of lesser acidity of said zeolite while the reactive sites of greater acidity remain in a substantially unassociated condition said catalyst being prepared by first treating the alumino-silicate zeolite with a Lewis ty-pe base selected from the group consisting of the nitrogen containing bases and the phosphorus containing bases under conditions such that the said base selectively and reversibly interacts with the acidic sites having a greater degree of acidity, then cornpositing the hydrogenation-dehydrogen component on the treated acidic component and reactivating the acidic sites by removing the basic compound from said acidic sites.
  • said acidic-component is an acidic crystalline alumino-silic-ate zeolite having a uniform pore size in the range between 6 to 15 Angstroms
  • said hydrogenation-dehydrogenation component is a metal selected from the class consisting of the Group VB, VIB, VIIB and VIII metals of the Periodic Table and said basic compound comprises ammonia.
  • said acidic component is acidic silica-alumina
  • said hydrogenation-dehydrogenation component is a metal selected from the class consisting of the Group VB, VIB, VIIB and VIII metals of the Periodic Table and said basic compound comprises ammonia.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • General Chemical & Material Sciences (AREA)
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US474996A 1965-07-26 1965-07-26 Catalyst compositions and process for preparation thereof Expired - Lifetime US3346510A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US474996A US3346510A (en) 1965-07-26 1965-07-26 Catalyst compositions and process for preparation thereof
GB30852/66A GB1146543A (en) 1965-07-26 1966-07-08 Improved catalyst compositions and process for preparation thereof
DE19661542122 DE1542122A1 (de) 1965-07-26 1966-07-22 Verfahren zur Herstellung von fuer die Umwandlung von Kohlenwasserstoffen geeigneten bifunktionellen Katalysatoren
FR70765A FR1487713A (fr) 1965-07-26 1966-07-25 Compositions catalytiques perfectionnées et leur procédé de préparation
NL6610507A NL6610507A (xx) 1965-07-26 1966-07-26

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6127300A (en) * 1997-01-27 2000-10-03 Asec Manufacturing General Partnership Process for making a catalyst with noble metal on molecular sieve crystal surface
US20100231546A1 (en) * 2007-11-28 2010-09-16 Koninklijke Philips Electronics N.V. Sensing device and method
WO2012146909A1 (en) * 2011-04-28 2012-11-01 Croda International Plc Process for producing monobranched fatty acids or alkyl esters

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2962435A (en) * 1956-12-14 1960-11-29 Union Oil Co Hydrocarbon cracking process and catalyst
US3140253A (en) * 1964-05-01 1964-07-07 Socony Mobil Oil Co Inc Catalytic hydrocarbon conversion with a crystalline zeolite composite catalyst
US3140251A (en) * 1961-12-21 1964-07-07 Socony Mobil Oil Co Inc Process for cracking hydrocarbons with a crystalline zeolite

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2962435A (en) * 1956-12-14 1960-11-29 Union Oil Co Hydrocarbon cracking process and catalyst
US3140251A (en) * 1961-12-21 1964-07-07 Socony Mobil Oil Co Inc Process for cracking hydrocarbons with a crystalline zeolite
US3140253A (en) * 1964-05-01 1964-07-07 Socony Mobil Oil Co Inc Catalytic hydrocarbon conversion with a crystalline zeolite composite catalyst

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6127300A (en) * 1997-01-27 2000-10-03 Asec Manufacturing General Partnership Process for making a catalyst with noble metal on molecular sieve crystal surface
US20100231546A1 (en) * 2007-11-28 2010-09-16 Koninklijke Philips Electronics N.V. Sensing device and method
US8525805B2 (en) 2007-11-28 2013-09-03 Koninklijke Philips N.V. Sensing device and method
WO2012146909A1 (en) * 2011-04-28 2012-11-01 Croda International Plc Process for producing monobranched fatty acids or alkyl esters
US8796480B2 (en) 2011-04-28 2014-08-05 Croda International Plc Process for producing monobranched fatty acids or alkyl esters
US8987488B2 (en) 2011-04-28 2015-03-24 Croda International, Plc Process for producing monobranched fatty acids or alkyl esters

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Publication number Publication date
GB1146543A (en) 1969-03-26
FR1487713A (fr) 1967-07-07
DE1542122A1 (de) 1970-03-26
NL6610507A (xx) 1967-01-27

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